CN113972369B - Ternary positive electrode material with high compaction density - Google Patents

Ternary positive electrode material with high compaction density Download PDF

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CN113972369B
CN113972369B CN202111271890.6A CN202111271890A CN113972369B CN 113972369 B CN113972369 B CN 113972369B CN 202111271890 A CN202111271890 A CN 202111271890A CN 113972369 B CN113972369 B CN 113972369B
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oxide
density
positive electrode
compaction
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CN113972369A (en
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苏美华
戚洪亮
王裕生
孙国征
罗帅
孟祥鹤
王尊志
于建
袁徐俊
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Ningbo Ronbay Lithium Battery Material Co Ltd
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract

The invention discloses a high-compaction-density ternary positive electrode material, which comprises the following raw materials in parts by weight: secondary ball: single crystal= (2-7): 1, the compaction density of the ternary positive electrode material under the pressure of 3.5T ranges from 3.55g/cm 3 ～3.86g/cm 3 The true density range is 4.70g/cm 3 ～5.10g/cm 3 The ratio of the compacted density at 3.5T pressure to its true density is between 0.72 and 0.81. The beneficial effects of the invention are as follows: the invention adopts the process of blending the secondary sphere single crystal, mixes the secondary sphere and the single crystal with proper proportion, and utilizes the characteristic that the size of the single crystal is far smaller than that of the secondary sphere to effectively fill gaps between the secondary spheres, so that the compaction density of the ternary positive electrode material prepared by the method can be obviously improved, the volume energy density of a battery can be effectively improved, and meanwhile, the cracking condition of the secondary sphere can be effectively reduced when the positive electrode material is used for preparing a pole piece.

Description

Ternary positive electrode material with high compaction density
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a high-compaction-density ternary positive electrode material.
Background
The new energy automobile is taken as an important direction of development of the automobile industry, the main resistance encountered at present is that the selling price of the new energy automobile is too high and the endurance mileage is insufficient, and the lithium ion battery has the advantages of being high in energy density, good in cycle performance, small in self-discharge rate, free of pollution, long in service life and the like, so that the lithium ion battery is widely applied to the new energy automobile, but the current lithium ion battery still cannot meet the demand of people for the endurance mileage, the volume energy density of the lithium ion battery can be effectively improved, the endurance mileage of the new energy automobile is effectively improved, the ternary positive electrode material is taken as a key core material of the lithium ion battery, the compaction density of the high-nickel ternary positive electrode material is improved, and the volume energy density of the lithium ion battery can be effectively improved, so that the demand of consumers for the endurance mileage is met.
At present, the volume energy density of the lithium ion battery is low, the volume energy density of the battery can be effectively improved by improving the compaction density, so that the endurance mileage of the electric vehicle is improved, and the requirements of consumers are met.
Disclosure of Invention
The main object of the application is to provide a ternary positive electrode material with high compaction density.
In order to achieve the above object, the present invention provides the following technical solutions:
the high-compaction-density ternary positive electrode material comprises the following raw materials in parts by weight: secondary ball: single crystal= (2-7): 1, a step of;
the general formula of the secondary sphere is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the average particle size of the secondary spheres (the average particle size of the secondary spheres measured under SEM (1 k)) ranges from 5.5 mu m to 14 mu m;
the single crystal has the general formula of Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0.2, N is one of Mn and Al, and the average grain diameter of the single crystal (the average grain diameter of the single crystal measured under SEM (5 k)) ranges from 1.5 mu m to 3 mu m;
the D50 of the volume distribution of the ternary positive electrode material meets the following conditions: d50 X is equal to or greater than 0.72 and equal to or less than 1.15;
the compaction density range of the ternary positive electrode material under the pressure of 3.5T is 3.55g/cm 3 ～3.86g/cm 3 The true density range is 4.70g/cm 3 ～5.10g/cm 3 The ratio of the compacted density at 3.5T pressure to its true density is between 0.72 and 0.81.
The electrode pole piece is prepared by the single secondary ball, because the particles of the secondary ball are larger than that of the single crystal, and a larger gap exists between the balls, the existence of the gap can lower the compaction density of the material, and meanwhile, the secondary ball is easy to crack in the process of manufacturing the battery pole piece; when the single monocrystal is used for preparing the electrode plate, because the grains of the monocrystal are smaller, gaps among the grains of the monocrystal are relatively more, and the compaction density of the material is lower due to the existence of more gaps; the invention adopts the process of blending the secondary sphere single crystal, mixes the polycrystal and the single crystal with proper proportion, and utilizes the characteristic that the size of the single crystal is far smaller than that of the secondary sphere to effectively fill the gap left by the secondary sphere, so that the compaction density of the ternary positive electrode material prepared by the method can be obviously improved, and meanwhile, the cracking condition of the secondary sphere can be effectively reduced when the positive electrode material is used for preparing a pole piece.
The average particle size is the average result obtained by taking n SEMs at a specific magnification. The average particle size of the secondary spheres and single crystals was measured using a Nano Measurer 1.2.
The high-compaction-density ternary positive electrode material is a preferable embodiment, wherein the secondary sphere consists of secondary sphere primary particles, and the general formula of the secondary sphere primary particles is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the particle size of the secondary sphere primary particles (the particle size of the secondary sphere primary particles measured under SEM (10 k)) ranges from 90nm to 950nm;
the monocrystal consists of monocrystal primary particles, and the general formula of the monocrystal primary particles is Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the single crystal primary particles are particlesThe diameter range is 500 nm-5 μm.
The high-compaction-density ternary positive electrode material, which is a preferred embodiment, comprises the following raw materials in parts by weight: 2-7 parts of secondary balls and 1 part of single crystal; the average particle diameter of the secondary spheres is 5.5-14 mu m, and the average particle diameter of the single crystal is 1.5-3 mu m.
Preferably, the positive electrode material is tested by a Markov 2000 laser particle size analyzer, wherein the D50 of the particle size volume distribution is 6-12 mu m, dmin is 0.45-1.5 mu m, dmax is 20-32 mu m, and the SPAN ((D90-D10)/D50) value of the volume distribution particle size is 0.6-1.7;
the specific surface area of the positive electrode material is 0.3m 2 /g～0.9m 2 Preferably, the specific surface area of the positive electrode material is: 0.40m 2 /g～0.60m 2 /g；
The positive electrode material is tested by adopting a buckling method, and the unit gram capacity value of the positive electrode material is 200 mAh/g-215 mAh/g under the condition of 0.2C charging and 0.2C discharging.
In a second aspect of the present invention, a method for preparing a high-compaction-density ternary cathode material is provided, comprising the steps of:
(1) Preparing a secondary ball;
(2) Preparing a single crystal;
(3) And mixing the secondary ball and the monocrystal at 20-25 ℃ for 6-30 min by using a batch mixer to obtain the high-compaction-density ternary positive electrode material.
In the process of preparing the ternary cathode material, the temperature of a drying room is kept at 20-25 ℃, the humidity is less than 5% Rh, the dew point is less than 25 Td/DEG C, the moisture of a finished product of the ternary cathode material is ensured to be lower than 250ppm, and the control of the moisture can reduce side reactions of a battery in the use process.
The preparation method of the ternary positive electrode material with high compaction density, which is a preferred embodiment, comprises the following steps:
step one, mixing and stirring a precursor, lithium salt and an additive N1 uniformly, and heating under an oxygen atmosphere to react to obtain an intermediate product;
and step two, washing the intermediate product with water, drying, and adding an additive N2 for secondary blending and back firing to obtain the secondary ball.
Preferably, in the first step, the precursor is nickel cobalt manganese hydroxide or nickel cobalt aluminum hydroxide, and the lithium salt is LiOH or Li 2 CO 3 The additive N1 is at least one of cobaltosic oxide, lanthanum oxide, magnesium oxide, yttrium oxide, cerium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide and aluminum oxide.
Preferably, in the first step, the heating temperature is 700-820 ℃, and the reaction time at the temperature is 8-15 h.
Preferably, in the second step, the drying is carried out for 3-8 hours under the condition of oxygen introduction and at the temperature of 120-160 ℃, and the additive N2 is at least one of alumina, zinc oxide, aluminum fluoride, boric acid, yttrium oxide, cobalt oxide, titanium oxide and tungsten oxide, and the content is 1000-5000 ppm;
the temperature of the secondary combustion is 250-600 ℃, and the time of the secondary combustion is 10-17 h.
The above-mentioned ternary positive electrode material with high compacted density, as a preferred embodiment, the preparation method of the single crystal comprises the following steps:
step one, mixing and stirring a precursor, lithium salt and an additive N3 uniformly, and heating under an oxygen atmosphere to react to obtain a primary sintering material of single crystals;
step two, washing the primary sintering material of the monocrystal, drying, and adding an additive N4 for secondary back firing to obtain the monocrystal.
Preferably, in the first step, the precursor is nickel cobalt manganese hydroxide, and the lithium salt is LiOH or Li 2 CO 3 The additive N3 is at least one of cobaltosic oxide, lanthanum oxide, magnesium oxide, yttrium oxide, cerium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide or aluminum oxide, the content is 3000 ppm-8000 ppm, the heating temperature is 850-950 ℃, and the reaction time is 15h～28h。
Preferably, in the second step, the drying is carried out for 3-8 hours under the condition of oxygen introduction and at the temperature of 120-160 ℃, and the additive N4 is at least one of alumina, zinc oxide, boric acid, yttrium oxide, cobalt oxide, titanium oxide and tungsten oxide, and the content is 1000-5000 ppm;
the temperature of the secondary combustion is 250-400 ℃, and the time of the secondary combustion is 10-17 hours;
the positive electrode material is tested by adopting a Markov 2000 laser particle size analyzer, wherein the D50 of the particle size and volume distribution is 6-12 mu m, dmin is 0.45-1.5 mu m, dmax is 20-32 mu m, and the SPAN ((D90-D10)/D50) value of the volume distribution particle size is 0.6-1.7;
the specific surface area of the positive electrode material is 0.3m 2/g-0.9 m2/g, preferably 0.40m 2/g-0.60 m2/g;
the positive electrode material is tested by adopting a buckling method, and the unit gram capacity value of the positive electrode material is 200 mAh/g-215 mAh/g under the condition of 0.2C charging and 0.2C discharging.
The beneficial effects of the invention are as follows: the invention adopts the process of blending the secondary sphere single crystal, mixes the secondary sphere and the single crystal with proper proportion, and utilizes the characteristic that the size of the single crystal is far smaller than that of the secondary sphere to effectively fill gaps left by the secondary sphere, so that the compaction density of the ternary positive electrode material prepared by the method can be obviously improved, the volume energy density of a battery can be effectively improved, and meanwhile, the cracking condition of the secondary sphere can be effectively reduced when the positive electrode material is used for preparing a pole piece.
Drawings
FIG. 1 is an SEM scan of a secondary sphere of example 1;
FIG. 2 is an SEM scan of a single crystal according to example 1;
FIG. 3 is an SEM scan of a ternary positive electrode material according to example 1;
FIG. 4 is an SEM scan of a pole piece made of the ternary positive electrode material described in example 1;
FIG. 5 is an SEM scan of a secondary sphere of example 2;
FIG. 6 is an SEM scan of a single crystal according to example 2;
FIG. 7 is an SEM scan of a ternary positive electrode material of example 2;
FIG. 8 is an SEM scan of a ternary positive electrode material of comparative example 1;
FIG. 9 is an SEM scan of a ternary positive electrode material of comparative example 2;
FIG. 10 is an SEM scan of a ternary positive electrode material of comparative example 3;
fig. 11 is an SEM scan of a pole piece made of the ternary positive electrode material described in comparative example 3.
Detailed Description
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described in the following in connection with examples, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.
Example 1
The high-compaction-density ternary cathode material of the embodiment 1 comprises the following raw materials in parts by weight: 3 parts of secondary balls and 1 part of single crystals;
the general formula of the secondary sphere is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the average particle size of the secondary spheres is 12.73 mu m;
the secondary sphere consists of secondary sphere primary particles, and the general formula of the secondary sphere primary particles is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the particle size range of the primary particles of the secondary spheres is 90-950 nm;
the single crystal has the general formula of Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0.2, N is one of Mn and Al, and the average grain diameter of the single crystal is 1.63 mu m;
the monocrystal consists of monocrystal primary particles, and the general formula of the monocrystal primary particles is Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the grain size of the primary particles of the single crystal is 500 nm-5 mu m.
The preparation method of the high-compaction-density ternary cathode material of the embodiment 1 comprises the following steps:
(1) Preparing a secondary ball:
step one, mixing and stirring a precursor (hydroxide of nickel, cobalt and manganese), lithium salt LiOH and an additive N1 cobaltosic oxide uniformly, and reacting for 15 hours under the condition of heating temperature of 760 ℃ in an oxygen atmosphere to obtain an intermediate product;
washing the intermediate product with water, drying for 5h at 120 ℃ under the condition of introducing oxygen, adding an additive N2 aluminum oxide to perform secondary blending and back firing, wherein the temperature of the secondary blending and back firing is 300 ℃, and back firing is performed for 10h at the temperature to obtain a secondary ball;
(2) Preparing a single crystal:
step one, mixing and stirring a precursor (hydroxide of nickel, cobalt and manganese), lithium salt LiOH and an additive N3 cobaltosic oxide uniformly, and reacting for 25 hours under the condition of heating temperature of 900 ℃ in an oxygen atmosphere to obtain a primary sintered material of single crystals;
step two, washing the primary sintering material of the single crystal, drying for 5 hours under the condition of oxygen introduction and 120 ℃, adding an additive N4 alumina to perform secondary back firing, wherein the temperature of the secondary back firing is 250 ℃, and back firing for 17 hours at the temperature to obtain the single crystal;
(3) And stirring and mixing the secondary ball and the monocrystal for 30min at the temperature of 20 ℃ to obtain the high-compaction-density ternary positive electrode material.
The 5-pass test of the high-density ternary cathode material described in example 1 has a compacted density as shown in Table 1, and the average compacted density of the 5-pass test is 3.68g/cm 3 The true density is tested by adopting a Kang Da Ultrapyc 5000 true density instrument, the true density testing method is a gas volume method, and the testing value is 4.93g/cm 3 。
TABLE 1
3.5T compaction test Test 1 Test 2 Test 3 Test 4 Test 5
PD/g/cm3 3.68 3.67 3.68 3.69 3.67
The ratio of the compacted density at 3.5T pressure to the true density is between 0.72 and 0.81.
Remarks: the 3.5T compaction density was measured by 1.5g, using a cylinder diameter of 12.95mm and a cylinder height of 32.2mm, starting from 0 to 3.5T, holding at 3.5T for 10s, then releasing pressure, measuring the volume V, and obtaining a 3.5T compaction density = 1.5g/V, with a compaction density in the range of 3.55g/cm 3 ～3.86g/cm 3 ；
The positive electrode material described in example 1 was tested by using a Markov 2000 laser particle sizer, wherein the particle size volume distribution D50 was 6 μm to 12 μm, dmin was 1.04 μm, dmax was 26.49 μm, and the SPAN ((D90-D10)/D50) value of the volume distribution particle size was 1.54;
the specific surface area of the positive electrode material is 0.4835m 2 /g；
The volume distribution D50 of example 1 above was 10.45 μm, satisfying: d50 The average particle size of the secondary sphere =x+ (1-X) the average particle size of the single crystal is 0.72.ltoreq.x.ltoreq.1.15.
The positive electrode material is tested by adopting a buckling method, and the unit gram capacity value of the positive electrode material is 206.3mAh/g under the condition of 0.2C charge and 0.2C discharge.
Example 2
The high-compaction-density ternary cathode material of the embodiment 2 comprises the following raw materials in parts by weight: 4 parts of secondary balls and 1 part of single crystals;
the general formula of the secondary sphere is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the average particle size of the secondary spheres is 6.71 mu m;
the secondary sphere consists of secondary sphere primary particles, and the general formula of the secondary sphere primary particles is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the particle size range of the primary particles of the secondary spheres is 90-950 nm;
the single crystal has the general formula of Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0.2, N is one of Mn and Al, and the average grain diameter of the single crystal is 1.63 mu m;
the monocrystal consists of monocrystal primary particles, and the general formula of the monocrystal primary particles is Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the grain size of the primary particles of the single crystal is 500 nm-5 mu m.
The preparation method of the high-compaction-density ternary cathode material of the embodiment 2 comprises the following steps:
(1) Preparing a secondary ball:
step one, a precursor (hydroxide of nickel cobalt manganese) and lithium salt Li 2 CO 3 Mixing and stirring additive N1 cobaltosic oxideUniformly stirring, and reacting for 13h under the condition of heating temperature of 750 ℃ in an oxygen atmosphere to obtain an intermediate product;
washing the intermediate product with water, drying for 4 hours at 130 ℃ under the condition of introducing oxygen, adding an additive N2 zinc oxide to perform secondary blending and re-firing, wherein the temperature of the secondary blending and re-firing is 300 ℃, and re-firing for 15 hours at the temperature to obtain a secondary ball;
(2) Preparing a single crystal:
step one, a precursor (hydroxide of nickel cobalt manganese) and lithium salt Li 2 CO 3 Mixing and stirring the additive N3 strontium oxide uniformly, and reacting for 15 hours at the heating temperature of 900 ℃ in an oxygen atmosphere to obtain a primary sintered material of the monocrystal;
step two, washing the primary sintering material of the monocrystal, drying for 5 hours under the condition of oxygen introduction and 120 ℃, adding an additive N4 tungsten oxide to perform secondary back firing, wherein the temperature of the secondary back firing is 250 ℃, and back firing for 17 hours at the temperature to obtain the monocrystal;
(3) And stirring and mixing the secondary ball and the monocrystal for 25min at the temperature of 20 ℃ to obtain the high-compaction-density ternary positive electrode material.
The 5-pass test of the high-density ternary cathode material described in example 2 has a compacted density as shown in Table 2, and the average compacted density of the 5-pass test is 3.72g/cm 3 The true density is tested by adopting a Kang Da Ultrapyc 5000 true density instrument, the true density testing method is a gas volume method, and the testing value is 4.90g/cm 3 。
TABLE 2
3.5T compaction test Test 1 Test 2 Test 3 Test 4 Test 5
PD/g/cm3 3.71 3.73 3.72 3.71 3.72
The ratio of the compacted density at 3.5T pressure to the true density is between 0.72 and 0.81.
Remarks: the 3.5T compaction density was measured by 1.5g, using a cylinder diameter of 12.95mm and a cylinder height of 32.2mm, starting from 0 to 3.5T, holding at 3.5T for 10s, then releasing pressure, measuring the volume V, and obtaining a 3.5T compaction density = 1.5g/V, with a compaction density in the range of 3.55g/cm 3 ～3.86g/cm3；
The positive electrode material described in example 2 was tested by using a Markov 2000 laser particle sizer, the particle size volume distribution D50 was 7.61 μm, dmin was 0.90 μm, dmax was 28.65 μm, and the SPAN ((D90-D10)/D50) value of the volume distribution particle size was 1.69;
the specific surface area of the positive electrode material is 0.5292m 2 /g；
The volume distribution D50 of example 2 above was 7.15 μm, satisfying: d50 The average particle size of the secondary sphere =x+ (1-X) the average particle size of the single crystal is 0.72.ltoreq.x.ltoreq.1.15.
The positive electrode material is tested by adopting a buckling method, and under the condition of 0.2C charge and 0.2C discharge, the unit gram capacity value is 203.7Ah/g.
Comparative example 1
The high-compacted density ternary cathode material of comparative example 1 is different from the ternary cathode material of example 2 in that: the weight ratio of the secondary spheres to the single crystal contained in the ternary positive electrode material of comparative example 1 is: 9 parts of secondary balls and 1 part of single crystals;
the general formula of the secondary ball is LinNiaCobM1-a-bO2, n is more than or equal to 0.95 and less than or equal to 1.10,0.75 and a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the average particle size of the secondary ball is 12.73 mu m;
the secondary sphere consists of secondary sphere primary particles, wherein the general formula of the secondary sphere primary particles is LinNiaCobM1-a-bO2, n is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the particle size range of the secondary sphere primary particles is 90-950 nm;
the general formula of the monocrystal is LimNacCodN 1-c-dO2, m is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the average grain diameter of the monocrystal is 1.63 mu m;
the monocrystal consists of monocrystal primary particles, wherein the general formula of the monocrystal primary particles is LimNacCodN 1-c-dO2, m is more than or equal to 0.95 and less than or equal to 1.15,0.80 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the particle size range of the monocrystal primary particles is 500 nm-5 mu m.
The preparation method of the high-compaction-density ternary cathode material of the comparative example 1 comprises the following steps:
(1) Preparing a secondary ball:
step one, mixing and stirring a precursor (hydroxide of nickel, cobalt and manganese), lithium salt LiOH and an additive N1 cobaltosic oxide uniformly, and reacting for 15 hours under the condition of heating at 750 ℃ in an oxygen atmosphere to obtain an intermediate product;
washing the intermediate product with water, drying for 8 hours at 120 ℃ under the condition of introducing oxygen, adding an additive N2 aluminum oxide to perform secondary blending and back firing, wherein the temperature of the secondary blending and back firing is 250 ℃, and back firing for 17 hours at the temperature to obtain a secondary ball;
(2) Preparing a single crystal:
step one, mixing and stirring a precursor (hydroxide of nickel, cobalt and manganese), lithium salt LiOH and an additive N3 cobaltosic oxide uniformly, and reacting for 15 hours under the condition of heating temperature of 900 ℃ in an oxygen atmosphere to obtain a primary sintered material of single crystals;
step two, washing the primary sintering material of the single crystal, drying for 8 hours under the condition of oxygen introduction and 120 ℃, adding an additive N4 alumina to perform secondary back firing, wherein the temperature of the secondary back firing is 250 ℃, and back firing for 17 hours at the temperature to obtain the single crystal;
(3) And stirring and mixing the secondary ball and the monocrystal for 30min at the temperature of 20 ℃ to obtain the high-compaction-density ternary positive electrode material.
The 5-pass test of the high-density ternary cathode material described in comparative example 1 has a compacted density as shown in Table 3, and the average compacted density of the 5-pass test is 3.50g/cm 3 The true density is tested by adopting a Kang Da Ultrapyc 5000 true density instrument, the true density testing method is a gas volume method, and the testing value is 4.83g/cm 3 。
TABLE 3 Table 3
3.5T compaction test Test 1 Test 2 Test 3 Test 4 Test 5
PD/g/cm3 3.50 3.50 3.49 3.49 3.50
The ratio of the compacted density at 3.5T pressure to the true density is between 0.72 and 0.81, and the average compacted density is slightly lower than the compacted density of the invention.
Comparative example 2
The high-compacted density ternary cathode material of comparative example 2 is different from the ternary cathode material of example 2 in that: the weight ratio of the secondary spheres to the single crystal contained in the ternary positive electrode material of comparative example 1 is: 0 part of secondary sphere and 1 part of monocrystal;
the method for producing the single crystal described in comparative example 2 was the same as that described in example 2.
The compacted densities of 5 tests of the high compacted density ternary cathode material described in comparative example 2 are shown in table 4. The average compaction density for 5 tests was 3.40g/cm 3 The true density is tested by adopting a Kang Da Ultrapyc 5000 true density instrument, the true density testing method is a gas volume method, and the testing value is 4.99g/cm 3 。
TABLE 4 Table 4
3.5T compaction test Test 1 Test 2 Test 3 Test 4 Test 5
PD/g/cm3 3.40 3.38 3.39 3.40 3.40
The ratio of the compacted density at a pressure of 3.5T to the true density is not between 0.72 and 0.81.
Comparative example 3
The high-compacted density ternary cathode material of comparative example 3 is different from the ternary cathode material of example 2 in that: the weight ratio of the secondary spheres to the single crystal contained in the ternary positive electrode material of comparative example 1 is: 3 parts of secondary sphere and 0 part of monocrystal;
the preparation method of the secondary ball described in comparative example 3 was the same as that of the secondary ball described in example 2 of the present application.
The 5-pass test of the high-density ternary cathode material described in comparative example 3 has a compacted density as shown in Table 5, and the average compacted density of the 5-pass test is 3.46g/cm 3 The true density is tested by adopting a Kang Da Ultrapyc 5000 true density instrument, the true density testing method is a gas volume method, and the testing value is 4.72g/cm 3 。
TABLE 5
3.5T compaction test Test 1 Test 2 Test 3 Test 4 Test 5
PD/g/cm3 3.45 3.46 3.46 3.47 3.47
The ratio of its compacted density at 3.5T pressure to its true density is between 0.72 and 0.81, but its true density is outside the scope of the invention.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (10)

1. A ternary positive electrode material with high compaction density is characterized in that,
the positive electrode material comprises the following raw materials in parts by weight: secondary ball: single crystal= (2-7): 1, a step of;
the general formula of the secondary sphere is Li n Ni a Co b M 1-a-b O 2 N is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a is more than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the average grain diameter of the secondary balls is 5.5-14 mu m;
the single crystal has the general formula of Li m Ni c Co d N 1-c-d O 2 M is more than or equal to 0.95 and less than or equal to 1.15,0.80, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0.2, N is one of Mn and Al, and the average grain diameter of the single crystal is 1.5-3 mu m;
the D50 of the volume distribution of the ternary positive electrode material meets the following conditions: d50 X is equal to or greater than 0.72 and equal to or less than 1.15;
the three-element positive electrode material has a compaction density of 3.55g/cm under a pressure of 3.5T 3 ～3.86g/cm 3 The true density range is 4.70g/cm 3 ～5.10g/cm 3 The ratio of the compacted density to the true density at 3.5T pressure is between 0.72 and 0.81;
the positive electrode material is tested by adopting a Markov 2000 laser particle size analyzer, wherein the D50 of the particle size and volume distribution is 6-12 mu m, dmin is 0.45-1.5 mu m, dmax is 20-32 mu m, and the SPAN ((D90-D10)/D50) value of the volume distribution particle size is 0.6-1.7;
the specific surface area of the positive electrode material is 0.3m 2 /g～0.9m 2 /g；
The positive electrode material is tested by adopting a buckling method, and under the condition of 0.2C charging and 0.2C discharging, the unit gram capacity value is 200 mAh/g-215 mAh/g;
the secondary sphere consists of secondary sphere primary particles, wherein the general formula of the secondary sphere primary particles is LinNiaCobM1-a-bO2, n is more than or equal to 0.95 and less than or equal to 1.10,0.75 and less than or equal to a and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, M is one of Mn and Al, and the particle size range of the secondary sphere primary particles is 90-950 nm;
the monocrystal consists of monocrystal primary particles, wherein the general formula of the monocrystal primary particles is LimNacCodN 1-c-dO2, m is more than or equal to 0.95 and less than or equal to 1.15,0.80 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, N is one of Mn and Al, and the particle size range of the monocrystal primary particles is 500 nm-5 mu m.
2. The high-compaction-density ternary positive electrode material according to claim 1, wherein the high-compaction-density ternary positive electrode material is a high-compaction-density ternary positive electrode material,
the positive electrode material comprises the following raw materials in parts by weight: 2-7 parts of secondary balls and 1 part of single crystal; the average particle diameter of the secondary spheres is 5.5-14 mu m, and the average particle diameter of the single crystal is 1.5-3 mu m;
the specific surface area of the positive electrode material is 0.40m 2 /g～0.60m 2 /g。
3. A process for preparing a high-density ternary positive electrode material according to any one of claims 1 to 2, characterized in that,
the method comprises the following steps:
(1) Preparing a secondary ball;
(2) Preparing a single crystal;
(3) And mixing and stirring the secondary ball and the monocrystal for 6-30 min at the temperature of 20-25 ℃ to obtain the high-compaction-density ternary positive electrode material.
4. The method for preparing the high-compaction-density ternary cathode material according to claim 3, wherein the method comprises the steps of,
the preparation method of the secondary ball comprises the following steps:
uniformly mixing a precursor, lithium salt and an additive N1, and heating in an oxygen atmosphere to react to obtain an intermediate product;
and step two, washing the intermediate product with water, drying, and adding an additive N2 for secondary blending and back firing to obtain the secondary ball.
5. The method for preparing a high-compaction-density ternary cathode material according to claim 4, wherein the high-compaction-density ternary cathode material is prepared by the method comprising the steps of,
in the first step, the precursor is hydroxide of nickel, cobalt and manganese, and the lithium salt is LiOH or Li 2 CO 3 The additive N1 is at least one of cobaltosic oxide, lanthanum oxide, magnesium oxide, yttrium oxide, cerium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide and aluminum oxide.
6. The method for preparing a high-compaction-density ternary cathode material according to claim 4, wherein the high-compaction-density ternary cathode material is prepared by the method comprising the steps of,
in the first step, the heating temperature is 700-820 ℃, and the reaction time at the heating temperature is 8-15 h.
7. The method for preparing a high-compaction-density ternary cathode material according to claim 4, wherein the high-compaction-density ternary cathode material is prepared by the method comprising the steps of,
in the second step, the drying is as follows: drying for 3-8 h at 120-160 ℃ under the condition of oxygen introduction, wherein the additive N2 is at least one of aluminum oxide, zinc oxide, aluminum fluoride, boric acid, yttrium oxide, cobalt oxide, titanium oxide and tungsten oxide;
the temperature of the secondary combustion is 250-600 ℃, and the time of the secondary combustion is 10-17 h.
8. The method for preparing the high-compaction-density ternary cathode material according to claim 3, wherein the method comprises the steps of,
the preparation method of the single crystal comprises the following steps:
uniformly mixing a precursor, lithium salt and an additive N3, and heating under an oxygen atmosphere to react to obtain a primary sintering material of the monocrystal;
step two, washing the primary sintering material of the monocrystal, drying, and adding an additive N4 for secondary back firing to obtain the monocrystal.
9. The method for preparing a high-compaction-density ternary cathode material according to claim 8, wherein,
in the first step, the precursor is hydroxide of nickel, cobalt and manganese, and the lithium salt is LiOH or Li 2 CO 3 The additive N3 is at least one of cobaltosic oxide, lanthanum oxide, magnesium oxide, yttrium oxide, cerium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide and aluminum oxide; the heating temperature is 850-950 ℃, and the reaction time at the heating temperature is 15-28 h.
10. The method for preparing a high-compaction-density ternary cathode material according to claim 8, wherein,
in the second step, the drying is carried out for 3-8 hours under the condition of oxygen introduction and at the temperature of 120-160 ℃, and the additive N4 is at least one of alumina, zinc oxide, boric acid, yttrium oxide, cobalt oxide, titanium oxide and tungsten oxide;
the temperature of the secondary combustion is 250-400 ℃, and the time of the secondary combustion at the temperature is 10-17 h.
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